JPS6151027A - Production of novel polyester resin - Google Patents

Abstract

PURPOSE:To produce a polyester resin having toughness, excellent abrasion resistance and flexibility, low setting temperature and blocking resistance, by polycondensing a specified diol component with a carboxylic acid component. CONSTITUTION:A diol component of formula I (wherein R<1> is a 2-4C alkylene and X and Y are positive integers provided that their sum has an average of 2- 16) is polycondensed with a carboxylic acid component comprising (a) 5- 30mol% dibasic carboxylic acid (anhydride) or its lower alkyl ester (e.g., fumaric acid), (b) 5-30mol% trimellitic acid (anhydride) or its lower alkyl ester and (c) 0.1-20mol% (i) polycarboxylic acid (anhydride) of an average MW of 8,000- 20,000 and a softening point of 60-120 deg.C, obtained by copolymerizing a 22-62C alpha-olefin with maleic anhydride or (ii) its lower alkyl ester and/or (iii) tetracarboxylic acid (anhydride) of formula II (wherein X is a 5-30C alkylene or alkenylene having at least one 3C or higher side chain).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for producing a new polyester resin that is strong, has excellent abrasion resistance, is flexible, has a low fixing temperature, and is difficult to cause blocking. .

[Conventional technology and problems]

The conventional method for producing polyester resin 7itm is to react a dicarboxylic acid with a diol having an etherified diphenol as its backbone to produce a linear polyester, and in addition to these two components, a third component is added to produce an etherified polyhydroxyl compound. ◇ Polyesters produced by these methods The resin has some good performance. However, linear polyester resins exhibit good solubility in unsaturated monomers but lack toughness and abrasion resistance, so their performance as cured polyesters is still insufficient. Further, although it can be used as a binder for toner used in electrophotography, it cannot be used in high-speed copying using Heat-Low 2- as the fixing method because an offset phenomenon occurs.

-For non-linear polyesters, polyester resins using etherified polyhydroxy compounds as the third component improve toughness and abrasion resistance while retaining some degree of solubility in unsaturated monomers, but Because the transition point is not high, there is a high risk of solidification, especially when used in powder form, making it difficult to use as a binder for glass fiber mats or as a binder for electrophotographic toners.

In addition, when using a polycarboxylic acid of tribasic acid or more as a third component, the effect is weak if the amount used is small, and it is effective if the amount used is increased, but on the contrary, it is hard and brittle, and has a high softening point. It cannot be used in hardened polyesters because it is insoluble in unsaturated monomers and cannot be used in hardened polyesters. In addition, during production, there is a risk of solidification in the reaction tank, which poses a risk of dust.

In addition, when polyester resin is used in powder coatings, powder adhesives, and electrophotographic toner binders, polyester resin is used in powder form, but in this case, from the viewpoint of energy conservation, it is necessary to apply it to the adherend at low temperatures. While it needs to be fixed, it must not cause blocking during storage.

[Means for solving problems]

The inventors of the present invention have arrived at the present invention as a result of intensive research to obtain a resin that satisfies all of these points.

That is, the present invention provides (a) the following general formula (wherein R1 is an alkylene group having 2 to 4 carbon atoms),
, Y must be positive integers, and the average value of their sum is between 2 and 16. ); (b) (a) divalent carboxylic acid or its acid anhydride or its lower alkyl ester; (1)) h! j Mellitic acid or its anhydride or its lower furkyl ester and (0) an average molecular weight a obtained by a copolymerization reaction of an α-olefin having 22 to 62 carbon atoms and maleic anhydride, having an o o o to 20,000 A copolymer of polycarboxylic acid, its acid anhydride, or its lower alkyl ester, or/and the following formula % formula % ((X is 5 carbon atoms having t-1 or more side chains with 3 or more carbon atoms)
S30 alkylene group or alkenylene group] A carboxylic acid component consisting of a tetracarboxylic acid, its acid anhydride, or its lower alkyl ester represented by S30, in which (b) accounts for 5 to 30 mol% of the total carboxylic acid component, (C) is 0.0% of the total carboxylic acid component. I S207%
In the present invention, examples of the diol component of polyoxypropylene (2,2) -2,2 -bis(4-hydroxyphenyl)propane, polyoxypropylene (3,3
) -2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene(2,0) -2,2-bis(
4-hydroxyphenyl)propane, polyoxypropylene (2,0) -polyoxyethylene (2,0) -
Examples include 2,2-bis(4-hydroxyphenyl)propane and polyoxypropylene (612,2-bis(4-hydroxyphenyl)propane).

In addition, among the carboxylic acid components of (1) in the present invention, (
Examples of the divalent carboxylic acids in a) include fumaric acid, maleic acid, 7-tar acid, n-dodecenylsuccinic acid, indodecenylsuccinic acid, n-dodecylsuccinic acid, indodecylsuccinic acid, n-octylsuccinic acid, and isooctylsuccinic acid. , n-octenyl succinic acid, n-butyl succinic acid, and the like.

By using alkyl or alkenyl succinic acid in combination with 7-maric acid, 7-tar acid, etc. as the above-mentioned divalent carboxylic acid, it is possible to lower the minimum fixing temperature without lowering the offset generation temperature, but the effect is small. Very soon, too many T
g decreases, making it difficult to control the reaction. Therefore, its content is preferably 5 to 30 mol% in the carboxylic acid component.

In addition, (b) trimellitic acid is a preferable acid component that improves the offset phenomenon, but if it is small, it is effective, but if it is large, it is difficult to control the reaction and it is difficult to obtain a polyester resin with stable performance. If the resin becomes hard and pulverized, undesirable phenomena such as an increase in the minimum fixing temperature occur if the resin is not separated. Therefore, the amount of trimellitic acid in the carboxylic acid component is preferably 5 to 30 mol%.

Furthermore, a relatively low molecular weight copolymer having an average molecular weight of 8,000 to 20,000 obtained by a copolymerization reaction of (0) an α-olefin having 22 to 62 carbon atoms and maleic anhydride has a copolymerization ratio of 8,000 to 20,000. is preferably α-olefin/maleic anhydride ratio of 1/4 to 4/1, and its softening point (
Ring and ball softening point according to λSTM-E 2 a-51T)
Examples of the olefins used include n-tococene-(1), n-tococene-(1), and preferably 60C to 120C.
+ Hemp Hsen-(1), n-todriacontin-(11, n-tetracontin-(1), n-pentatetracontin-(1), n-pentacontin-(1),
n-hexacocytene-(1),3-butylde;sen-(
1), 5-ethylhexacosene-(1), and the like.
Hexa;Cef-(81 and other inner olefins can also be contained, but since the toner will be more likely to cake,
It can be contained up to 10% by weight in the olefin. By using such polycarboxylic acids, it is possible to improve offset resistance without raising the minimum fixing temperature in the fixing process, but if used in large quantities, toner caking is likely to occur, resulting in less reaction and less force. becomes difficult to control. Therefore, its content in the carboxylic acid component is 0.1 to 20%, more preferably 1 to 1%.
It is 0 mol%.

When producing the polyester resin of the present invention, the ratio of the number of hydroxyl groups in the diol component to the number of carboxyl groups in the carboxylic acid component is 1.2 to 0.8, preferably 1.1 to 0.9. It's good to do that.

Furthermore, the compound represented by the formula (I) used in the present invention (
C) tetracarboxylic acids include (1) 4-neobentrizonyl-1,2,6,7-heptanetetracarboxylic acid (2), 4-neopentyl-1,2,d,7-hebutene (4); )-tetracarboxylic acid (3) 3-methyl-4-heptyl-1,2,5,6-
Hexanetetracarboxylic acid (4) 6-methyl-3-heptyl-5-methyl-1,2
,6,7-he1ten(4)-tetracarboxylic acid(5)3
-nonyl-4-methylisonyl-1,2,5,6-hexanetetracarboxylic acid (6) 3-desylizonyl-1,2,5,6-hexanetetracal, 3-nonyl-1,2 ganic acid (7) , 6, Huheptene (4)-
Tetracarboxylic acid C3) 3-decenyl-1,2,5,6-hexanetetracarboxylic acid (9) 3-butyl-3-ethylenyl-1,2,5,6-
Hexanetetracarboxylic acid αυ 3-methyl-4-butyrisonyl-1,2,6,7
-Hebutanetetracarboxylic acid α1) 3-Methyl-4-butyl-1,2,6,7-heptene (4)-Tetracarboxylic acid α23-Methyl-5-octyl-1,2,6,7-heptene ( 4)-tetracarboxylic acid and the like. The structural formulas of these compounds are shown below. For convenience, all are shown in the form of acid anhydrides.

0 0 o 0 By using these tetracarboxylic acids, the minimum fixing temperature can be lowered considerably in the fixing process, and the offset resistance can be improved, but in small amounts, they are not effective. If too little is used, fixing properties will deteriorate if too much is used, and it will be difficult to control the degree of resin polymerization during production.

Therefore, its content is carbo/g, 0.1 to 20 in the ingredients.
It is preferably 1% to 10% by mole, more preferably 1 to 10% by mole.

Also, similar tetracarboxylic acids include aliphatic tetracarboxylic acids without side chains or aliphatic tetracarboxylic acids with very short side chains, such as +"J'1,2,7.8-octanetetracarboxylic acid, 1 .2,5.6-hexanetetracarboxylic acid, 1,2゜11.12-dodecanetetracarboxylic acid, 3-methyl-1,2,10,11-undecanetetracarboxylic acid, 4-ethyl-1,2, Examples include 7,8-octene(4)-tetracarboxylic acid, but those with 3 carbon atoms
It is not as effective on low-temperature fixing properties as the tetracarboxylic acids having one or more of the above side chains, and increasing the amount used tends to cause toner caking and makes it difficult to control the rapid reaction, which is not preferable. Also, alicyclic polycarboxylic acids, aromatic tetravalent carboxylic acids, such as 3-methyl-5-succinyl-4-cyclohexene-1,2-dicarboxylic acid, pyromellitic anhydride, be/cyphenonetetracarboxylic acid, cyclo Bentenetetracarboxylic acid, mel-7aninic acid, and the like often cause decomposition, sublimation, coloring, etc. during resin production, and are less effective in low-temperature constant N properties and offset resistance.

The polyester resin used in the present invention is prepared by combining a polyhydric carboxylic acid component and a polyol component in an inert gas atmosphere.
It can be produced by polycondensation at a temperature of ~250C. At this time, commonly used esterification catalysts such as zinc oxide, stannous oxide, diptyltin oxide, diptyltin dilaurate, etc. can be used to accelerate the reaction. It can also be produced under reduced pressure for the same purpose.

The polyester resin produced according to the present invention can be used for various purposes, but is particularly useful as a binder, and is also used in powder form, such as powder coatings, powder adhesives, and electrophotographic toners. It is convenient for applications such as industrial binders.

The resin produced according to the present invention can be mixed with other chemical substances such as pigments, dyes, and magnetic powders depending on the purpose. Examples of colorants used in combination with the resin produced according to the present invention include carbon black, acetylene black, phthalocyanine blue, Hermanent Brown FC, brilliant first scarlet, Pigment Green B10-Damine-B base, and Nlupen. Trend 49, Nrupent Red 146, Nrupent Plue 35, Iron Black, Nigrosine, Benzidine Ie 4-, Quinacridone, Rhodamine B, 7 Talocyanine Plue, Nicrosheen Dye, Aniline Blue, Cal; Oil Blue, Claw Thousand Yellow, Ultramarine Blue, Examples include DuPont oil red, quinoline yellow, methylene blue, chloride/malachite green oxalate, rose bengal, and mixtures thereof. Examples of the magnetic material used in the present invention include ferromagnetic materials such as ferrite and magnetite. The magnetic material has an average particle size o, i~
It can be used by dispersing 40 to 70% by weight of Yu in a resin in the form of a 1 micron fine powder.

Furthermore, when the resin produced by the production method according to the present invention is used in an electrophotographic toner binder, it acts as a binder for binding various components used for producing the toner, and for example, Purchase toner along with colorant, magnetic material, anti-offset agent, charge control agent, etc.

In this case, the following compounds, for example, can be used as the charge control agent.

(I) R R: hydrogen, lower alkyl group, lower alkoxy group, and hap
A group selected from the group consisting of gen.

R1: a group selected from the group consisting of hydrogen, a lower alkyl group, a lower alkoxy group, and a halogen.

R2, R5: a deci group, an imino group bonded to a substituent selected from an aryl group, an aryl alkenyl group, a substituted 7-aryl group, and a substituted aryl alkenyl group represented by the following general formulas (1) to (3). and alkenyl groups.

(In the formula, R4 is a group selected from the group consisting of hydrogen, a lower dialkylamino group, a nido og, a low a alkoxymorpholino group, a pivelinodino group, a halogen group, and a julolidino group, and n is a to 3 m is an integer of 1 to 4.) show.

Alternatively, the following compound R1 = hydrogen, hydroxyl group, alkenyl group, or alkyl group R3 to R6 = hydrogen, alkyl group, allyl group, aralkyl group, or alkenyl group The content of this compound in the resin is 0.1 to 15% by weight. It is preferably 0.8 to 5% by weight. Content is 0
．． If it is less than 2% by weight, the stability of the charge will be lost, and if it becomes 15% by weight, the charge amount will be saturated, and there will be no effect even if it is added more than that, and on the contrary, it will affect other electrophotographic physical properties. adversely affect.

The above-mentioned compound will be specifically shown below, but the present invention is not limited to this example.

General formula ω Ar3 where Ar4. Ar2 and Ar represent a substituted/unsubstituted aromatic carbocycle or a substituted/unsubstituted aromatic heterocycle, and A
r1. At least one of Ar2 and A r s is an electron-donating group, and n represents 0 or 1.

Preferred pyrazoline derivatives are those represented by the following general formula (n).

General formula 0 In the formula, Ar3 represents a substituted/unsubstituted aromatic polycyclic group or a substituted/unsubstituted aromatic heterocyclic group, R1, R2, R3
and R4 is a substituted/unsubstituted alkyl group, or a substituted/unsubstituted alkyl group.
It may be an unsubstituted 7-aryl group or may form a ring together with a nitrogen atom, R1°R2, R5 and R4 may be the same or different, and n represents 0 or 1. Note that the ruamino group, diethylamino group, and meteroethyl group in the general formula [V] include, for example, electron-donating groups such as a morpholino group, a piperidino group, a piperazino group, and a pyrrolidino group, and A r 3. Examples of such groups include substituted and unsubstituted phenyl groups, naphthyl groups, anthranyl groups, pyridyl groups, and quinolyl groups.

□-E(1), 1lcF(1)f;yf:h4 k”
Specific examples of the 5 y"Ij y" conductor include those having the following structural formula.

Also, a piperazine derivative represented by the following general formula (1)
1 may also be used.

General formula (1) In the formula, Ar represents a substituted/unsubstituted aromatic carbocyclic group or a substituted/unsubstituted aromatic heterocyclic group, and preferably has an electron-donating substituent. R is a hydrogen atom or a substituted
Represents an unsubstituted lower alkyl group or aryl group. Ar
Examples of the substituent include a substituted or unsubstituted phenyl group, naphthyl group, anthranyl group, pyridyl group, or quinolyl group, and preferably an electron-donating substituent, such as a dimethylamino group, a diethylamino group, a methyl- dithylamino group, morpholino group, piperidino group,
Piperazino 56 or pyrrolidino groups are more preferred.

R represents a hydrogen atom, an unsubstituted/substituted lower alkyl group (eg, methyl group, ethyl group, butyl group, propyl group, etc.), or an aryl group (eg, phenyl group).

Specific examples of the piperazine fatty conductor represented by the general formula (1) include those having the following structural formula.

(81C2H3-N w-C>cH2Q convex-0□H5℃
-) Compounds represented by the general formula of the C-grammar can also be used (wherein R represents a substituted or unsubstituted aromatic ring or heterocycle). Examples include the following: 0 compound boiled e 3 HCCH.

HCCH33 Furthermore, a compound R4 of the following general formula I (wherein R1, R2, R, and R4 represent an alkyl group or an aralkyl group, and may be the same or different) or the following general formula 1 Compound R (in the above formula, R3, R4 and R5 represent an alkyl group or an aralkyl group, and may be the same or different.

) may also be used.

Typical specific examples of the compound represented by the general formula (IJ) include the following.

(:;2H5 H3 Further, as the compound represented by the general formula (1), the following compounds are exemplified.

2H5 Alternatively, the following compounds may also be used.

However, R7-R4: H1 CnH2n+1 (n = 1 to 3) respectively R5, R6: 0nH2n+ 1 (n = 1 to 3)
Or (represents La.

The ratio of the above compounds contained in the toner is o
, itt% or more, preferably 0.3% by weight or more.

Compounds of the general formula of the grammar may also be used.

However, R1: hydrogen, methyl group, ethyl A-group, chloroethyl group,
Or, hydroxyethyl group R2: hydrogen, lower alkyl group such as methyl group, ethyl group, aralkyl group such as benzyl group, phenyl group, or aromatic group such as naphthyl group R3: lower alkyl group such as methyl group, ethyl group, etc. group, substituted alkoxy groups such as methoxy group, ethoxy group, chloro,
A halogen such as bromine or a nitro group is used in the present invention as a charge control agent for the toner.

I can give you something.

I 2H5 αG 2H5 2H5 2H5 H2COOOH.

Alternatively, a compound represented by the following formula can be used.

・・・・・・・・・(a)-(1) ・・・・・・・・・(70-(21) ・・・・・・・・・((a)-(3) ・・・・・・・・・(Low-(1) ・・・・・・・・・(b)-(2) ・・・・・・・・・(B)-(3) ・・・・・・・・・← Ra (1) ・・・・・・・・・(/i　−＜21 ・・・・・・・・・(/1-(3) Alternatively, a compound represented by the following formula may also be used.

(In the above formula, R7, R2, R represent an aromatic ring such as a benzene ring or a naphthalene ring with or without a substituent, and n represents an integer of 0 or 1.) Charge adjustment in the present invention Typical specific examples of compounds of the above general formula used as agents include the following: 〇 or the following compound X.

- B Suitable divalent metal ions include B, 2+, M, 2+, ca2+, 2+
, sn2+, Pb2+, F62+, c02+.

These include Ni and Zn. In addition, trivalent ions include kl, 19c, Fe, Go,
Ni, Or.

There are Y3+ etc. Examples of salicylic acid or derivatives thereof that form coordinates or counterions with the above metal ions include salicylic acid, salicylamide, salicylamine, salicylaldehyde, salicyrosalicylic acid, and ditertiarybutylsalicylic acid.

Or AI! , Ba, Ca, Cd, Co, Or, Ci
u, Fe, Hg, Mg.

Carboxylate salts, alkoxylates, organometallic complexes, and chelate compounds of polyvalent metals such as Mn, N, Pb, Sn, Sr, and Zn can be used. Examples include zinc acetate, magnesium acetate, calcium acetate, aluminum acetate, magnesium stearate, calcium stearate, aluminum stearate, aluminum isopropoxide, aluminum acetylacetonate, iron (n
) acetylacetoner), 3.5 chromium di-tert-butyl stearate, basic aluminum acetate, zinc stearate, aluminum n-butoxide, aluminum n-butoxide, monosec butoxyaluminum diisoproboxide, aluminum methoxide , aluminum tris(ethylacetoacetate), nickel acetylacetonate, iron acetylacetonate, etc.

〔Example〕

Examples will be described in detail below, but the present invention is not limited to these examples.Example-1 Polyoxypropylene (2,2) -2,2-bis(4)
-Hydroxyphenyl)furopane 525, F.

Polyoxyethylene(21-2,2-bis(4-hydroxyphenyl)furopane 487.5F, 77-ruic acid 1)
72,5 F, inoctylsuccinic acid 138I and hydroquinone 0.11 in glass! The mixture was placed in a JJ2-e four-bottle flask, equipped with a thermometer, a stainless steel stirring bar, a flowing-down condenser, and a nitrogen inlet tube, and reacted with stirring at 200 C in a nitrogen stream in an electric heating mantle.

When the acid value is measured when water stops flowing out, it is 1.
It was o wry KOH/i.

Furthermore, anhydrous trimellit e11s, 2i and average carbon number 6
A copolymer of 50% by weight of α-olefin No. 2 and 50% by weight of maleic anhydride (average molecule: fa' 8*000, softening point 601Z'') was added with 21.3N and reacted for about 8 hours until the acid value decreased. The reaction was terminated when the reaction reached 25 ■KOH/Ji'.The resulting resin was a pale yellow solid with a softening point of 122C at the time of termination.

Even when this resin was pulverized and left at 45C for one month, no blocking occurred. To 100 parts of the resin, 8 parts of carbon black, 8 parts of Long Bien Carbon Co., Ltd. (Ben 3500) and a chromium-containing charge control agent (Orient Chemical Co., Ltd.) were added.
Two parts of Pontron 554) were milled in a ball mill, kneaded with three rolls, coarsely crushed in a cooling layer, finely pulverized in a jet mill, and a toner having an average particle size of 12 μm was produced using an air classifier.

100 parts of this toner and 1200 parts. P iron powder (Japanese iron powder g
E F V 200/s o ) was uniformly stirred in a blender to prepare a developer. A clear image with no spot stains was obtained using a commercially available copying machine.

Modifying the constant Mc1-2- temperature of the commercially available copying machine to make it variable1
Images were produced at temperatures ranging from 00C to 240C. The results are shown in Table-1.

Fixability was evaluated using cellophane tape peel test: 120C
Example 2 No peeling of the fixed toner was observed even with polyoxypropylene (2,2) -2,2-bis(4
-hydroxyphenyl)propane 1000j, terephthal fi237,1, Ii', n-dodecylsuccinic acid 286. F, 0.5I of stannous oxide, and 0.19I of Is hydroquinone were placed in the same apparatus as in Example-1, and reacted at 260C in a nitrogen stream.

When the acid value is measured when water stops flowing out, it is 1.
It was 5■KOH/I.

Furthermore, anhydrous Trimerit 15254.9. F and 30% by weight of α-olefin having an average carbon number of 45 and maleic anhydride 7
Copolymer B (average molecular weight i o, o o o
, softening point 75C')29. F was added and reacted for about 8 hours, and the reaction was terminated when the softening point reached 1250.

The resulting resin was a pale yellow solid with an acid value of 16 m9KOH/I. Even when this resin was crushed and released for 4501 months, no blocking occurred.

In the same manner as in Example 1, the offset occurrence temperature and minimum fixing temperature were measured. The results are shown in Table 1.

Examples 3 to 5, Comparative Examples 1 to 5 Next, Table 1 shows several examples and comparative examples using polyester resins synthesized by a method similar to Example 1.

Example-6 Polyoxypropylene (2,2) -2,2-bis(4
-Hydroxyphenyl) furopane 5259, polyoxyethylene (21-2,2-bis(4-hydroxyphenyl) tetrapane 488 &, 7 maric acid 1599, trimellitic acid 126,9,3-indecenyl-1,2,5 ,6
-Hexanetetracarboxylic acid 60y, indodecenylsuccinic acid 1701 and 1.5! Place the hydroquinone (I) in a four-glass 1J24 flask, and remove the thermometer, stainless steel stirring bar, flowing condenser, and phoneme inlet tube)
Heat to 2000" in an electric heating mantle under nitrogen flow.
'C The reaction was carried out with stirring. The degree of polymerization is ASTME28
The softening point was tracked according to -51T, and the softening point was 1.
The reaction was terminated when 22C was reached. The resulting resin was a pale yellow solid: j5. The glass transition temperature measured by DSO (differential calorimetry) was 62C.

Comparative Example-6 A resin was produced using the same equipment and procedure as in Example 6 except that 3-indecenyl-1,2,5,6-hexanetetracarboxylic acid was removed, and when the softening point reached 1220. The reaction has ended. The obtained resin was a pale yellow solid) and had a glass transition point of 62C.0 Examples 7 to 12, Comparative Examples 7 to 10 A polyester resin synthesized in a manner similar to Example 6 was used. Several examples and comparative examples are shown in Table-2.

Note) BPA (2,2)PO: Polyoxypropylene (2,2) -2,2-bis(4-hydroxyphenyl) Propane Blue 2BPA (21EO: Polyoxyethylene 7 (21
-2,2-bis(4-hydroxyphenyl)propane 5 BPA (61PO: Polyoxypropylene (6
)-2,2-bis(4-hydroxyphenyl)propanthene 4FA: fumaric acid 5TPA: terephthalic acid 6 PA=isophthalic acid 7 Alkyl, alkenyl succinic acid Y (A): indodecenyl succinic acid 284 (B)
: Isooctylsuccinic acid 228 (C:) :
n-dodecenylsuccinic acid 284 TMA: trimellitic anhydride 9 Tetracarboxylic acid (P): 3-Isodecenyl-1,2,5,6-hexanetetracarboxylic acid @): 4-Neopentyl-1,2,6 ,7-heptene(4)-tetracarboxylic acid (R): s-methyl-5-octyl-1,2,6,
7-hepte/(4)tetracarboxylic acid (s): 4-ethyl-1,2,7,8-octene (
4)-Tetracarbo/acid

Claims (1)

[Claims] 1 (a) The following general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R^1 is an alkylene group having 2 to 4 carbon atoms,
X and Y are positive integers, and the average value of their sum is 2 to 16
It is. ) and (b) (a) divalent carboxylic acid or its acid anhydride or its lower alkyl ester, (b) trimellitic acid or its acid anhydride or its lower alkyl ester, and (c) Average molecular weight 8, obtained by copolymerization reaction of α-olefin having 22 to 62 carbon atoms and maleic anhydride.
000 to 20,000 copolymer of polycarboxylic acid, its acid anhydride, or its lower alkyl ester, or/and the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (X has 3 or more carbon atoms 5 or more carbon atoms with one or more side chains of
30 alkylene group or alkenylene group) A carboxylic acid component consisting of a tetracarboxylic acid or an acid anhydride thereof or a lower alkyl ester thereof, in which (b) is 5 to 30 mol% of the total carboxylic acid component, A method for producing a novel polyester resin, comprising condensation polymerization of (c) with a carboxylic acid component in an amount of 0.1 to 20 mol% of the total carboxylic acid components.